(N,-dimethyl-N-{8 3-methylmetalolycarbamyloxy)-phenyl{9 -urea

ABSTRACT

WHERE R4 is hydrogen or alkyl, R5, hydrogen or alkyl, R6, alkyl or alkoxy, R5 and R6 are jointly with the N atom a heterocyclic ring possibly containing additional N and/or O atoms, AND X is oxygen or sulfur and, if B represents hydrogen, R2 may also represent alkyl or alkenyl, possess a herbidical effect and are suitable in particular for weed control in crop cultivations.   WHERE R1 is hydrogen or alkyl, R2, aryl, aralkyl, or cycloakly possibly mono- or polysubstituted by alkyl and/or halogen alkyl and/or alkoxy and/or alkyl mecapto and/or halogen and/or the nitro group, R3, hydrogen or alkyl, A and B are different and represent hydrogen or the radical   Agents having at least one compound of the general formula

United States Patent 1 91 Boroschewski et al.

[ Apr. 22, 1975 [54] (N,N-DI1\/[ETHYL-N- [3-METHYLMETALOLYLCARBAMYLOXY)- PHENYL1-UREA [75] Inventors: GerhardBoroschewski; Frederich Arndt; Reinhard Rusch, all of Berlin, Germany[73] Assignee: Schering AG, Berlin and Bergkamen, Germany 22 Filed: July10, 1970 [21] App]. No.: $3,988

Related US. Application Data [63] Continuation of Ser. No. 663,938, Aug.29, 1967,

abandoned.

[30] Foreign Application Priority Data Sept. 5, 1966 Germany 39491 June7, 1967 Germany 40838 [52] US. Cl 260/471 C; 71/88; 71/94;

[51] Int. Cl. C07c 101/18 [58] Field of Search 260/471 C [56] ReferencesCited UNlTED STATES PATENTS 10/1968 Wilson et al. 260/471 C 3/1969Wilson et al.... 260:71/471 C;l20 X Primary Examiner-Alex MazelAssistant Examiner-Jose Tovar 57 ABSTRACT Agents having at least onecompound of the general formula where R is hydrogen or alkyl,

R aryl, aralkyl, or cycloakly possibly monoor poly-substituted by alkyland/or halogen alkyl and/0r alkoxy and/or alkyl mecapto and/or halogenand/or the nitro group,

R hydrogen or alkyl,

A and B are different and represent hydrogen or the radical 1 Claim, NoDrawings (N ,N-DIMETHYL-N- [3-METHYLMETALOLYLCAR- BAMYLOXY)-PHENYL]-UREAThe invention relates to herbicides. It relates in particular toherbicides having a selective herbicidal effect, containing newN-carbamoyloxy-phenylureas.

The herbicidal effect of 3-(Nalkylcarbamoyloxy)- phenylureas, e.g.N,N-dimethyl-N-(3-(N"-tertiary butylcarbamoyloxy)-phenyl)urea, isdiscussed in known Belgian Patent No. 661,399. These compounds, howwhereR, is hydrogen or alkyl,

R aryl, aralkyl, or cycloakyl possibly monoor polysubstituted by alkyland/or halogen alkyl and/or alkoxy and/or alkyl mecapto and/or halogenand/or the nitro group,

R hydrogen or alkyl,

A and B are different and represent hydrogen or the radical 41f CX Nwhere R, is hydrogen or alkyl, R hydrogen or alkyl,

R alkyl or alkoxy,

R and R are jointly with the N atom a heterocyclic ring possiblycontaining additional N and/or 0 atoms,

and

Name of Compound X is oxygen or sulfur and, if B represents hydrogen,

R may also represent alkyl or alkenyl, possess a herbicidal effect andare suitable in particular for weed control in crop cultivations.

Thus, with their use, contrary to the above named known activeingredients, delicate dicotyledons, for example, sugar beets and cotton,are surprisingly enough not harmed, This selective effect extends to theuse both in the pre-germination process as by spraying on seed, and tothe use in the post-germination process, by treatment of the germinatedcultures, so that there is present here a true selectivity as to effect.The tolerance of the crop plants toward the agents to be used accordingto this invention is considerable, as even major quantities up to 5 kgof active ingredient per hectare cause no damage to the crops.

Considerable technical progress is therefore connected with the use ofthe herbicides according to the invention, since because of the greatselectivity of these herbicides a reliable control of weeds in beet andcotton cultivations without damage to these crops, is rendered possible.

It is obvious that the herbicides according to the invention aresuitable not only for selective weed control,

but they also can be used in adequate dosages for the destruction of anyundesirable plant growth.

As active ingredients; suitable for the above indicated purposescompounds within the above stated general formula and sharing thefollowing characteristics: R is phenyl, 2-,3-,4-tolyl,2,3-dimethylphenyl, 2,4- dimethylphenyl, 2-,3-,4-chlorophenyl,4-fluorphenyl, 4-bromophenyl, 4-iodophenyl, 3,4-dichlorophenyl,2,5-dichlorophenyl, 3-chloro-4-methylphenyl, 3-trifluoromethylphenyl,4-nitrophenyl, 4-methoxyphenyl, 4-methylmercaptophenyl, alpha-naphthyl,benzyl, 4- chlorobenzyl, alkyl radicals with up to 10 carbon atoms, asmethyl, ethyl, alkyl, propyl, isopropyl, etc., cycloalkyl, radicals,such as cyclohexyl and others; R R R and R are each in itself, hydrogenor low alkyl, as methyl or ethyl or ethyl, and others; R is a low alkylor low alkoxy, as methyl, ethyl, methoxy or ethoxy and others; R and Rjointly with the N atom are the morpholino, piperidino, or pyrrolidinogroup and others, and X is oxygen or sulfur.

Examples of compounds usable according to the invention are thefollowing (Fp. means melting point):

Physical constant N,N-dimethy Fp. 174 l75,5C

Fp. 96 97C Fp.= 151 152C Fp.= 129 -c (4'-methylp enyl)-carbarnoyloxy)-phenyl )-urea Fp.= 154- 155C Fp. 96 97C methylphenyl )-carbamoyloxy)-phenyl )-urea Fp. I29 130C (3'-methyl henyl)-carbamoyloxy)-phenyl)-thiourea resinified N"-(2'-methylphenyl )-carbamoyloxy)-phenyl)-urea Fp. 162 163C N'-( 3'-methylphenyl)-carbamoyloxy)-phenyl)urea Fp. l62,5 l63,5C

carbamoyloxy)-phenyl)-urea Fp. 167 168C The new active ingredients to beused according to the invention may be produced, for example,accordingto the following illustrative processes:

By reaction of hydroxyphenyl ureas or thioureas of the general formulapossibly in the form of the alkali, e.g. of the solium or potassiumsalt, (a) with isocyanates of the general formula advantageously in anorganic solvent, as for example, tetrahydrofurane or dimethyl formamide,and possibly with addition of a catalyst, preferably an organic base, asfor example, triethylamine, or (b) with carbamoyl chlorides of thegeneral formula advantageously in an organic solvent, e.g. pyridine, andpossibly with addition of an organic or inorganic base, e.g.triethylamine, or (c) with phosgene, advantageously with the use of anorganic solvent, e.g. tetrahydrofurane, acetic ester or ethylenechloride, and possibly with addition of an inorganic or organic base,e.g. soda lye or N,N-dimethyl aniline, to the corresponding chloroformicacid ester, which is then reacted with a compound of the general formulaadvantageously at temperatures between 5 C and room temperature in wateror in an organic solvent, e.g. acetic ester or tetrahydrofurane, ifdesired with addition of an acid-binding agent, as for example, theabove-named bases, or alkali or alkaline earth oxides, hydroxides, orcarbonates, R R R A, B, and X having the above mentioned meaning in thestated general formulas.

The following examples illustrate the production of the new activesubstances, without limitation thereto.

1. Preparation ofN,N-dimethyl-N'-(3-(3-methy1phenyl)-carbamoyloxy)-phenyl)-urea 18.0 g(0.1 mole) of N,N-dimethyl-N'-(3- hydroxyphenyl) urea are dissolved in amixture of 25 ml ofdimethyl'formamide and 50 ml of tetrahydrofurane andthe solution is added with 0.5 ml of triethylamine and 13.3 g(0.1 mole)of 3- methylphenylisocyanate. After 2 hours at room temperature, thesolution is added with 400 ml of ether, whereupon the carbamatecrystallizes out.

Yield: 26.3 g 84% of the theory N: calculated 13.42% found 13.34%

2. Preparation of N,N-dimethy1-N-( 3-(N"-methyl-N"-(3'-methylphenyl)-carbamoyloxyphenyl)-urea The sodium salt produced from 9.0g of N,N- dimethyl-N'-(3-hydoxyphenyl)-urea is taken up in 50 ml ofacetonitrile. While stirring, 9.2 g of N-methyl-N-(3-methylphenyl)-carbamoylchloride in portions are added at 25 C.Stirring is continued for 30-minutes at 50 C. After cooling to roomtemperature, the solution is poured into about 20 ml of water, whereuponthe carbamate crystallizes out.

Yield: 14.3 g 87.5% of the theory m.p.: 126 C i 3. Preparation ofN,N-dimethyl-N -(4-( N "-phenylcarbamoyloxy)- phenyl)-urea 12.6 g (0.07mole) of N,N-dimethyl-N'-4-(hydroxyphenyl)urea are dissolved in ml oftetrahydrofurane and the solution added with 0.5 ml of triethylamine and8 ml of phenylisocyanate. After several hours at room temperature, thecarbamate crystallizes out upon additi'on of light gasoline.

Yield: 20.9 g 99.8% of the theory m.p.: 172 174 C 4. Preparation ofN,N-dimethyl-N'-(4-(N-methyl-N"-phenylcarbamoyloxy)-phenyl)-urea Thesodium salt produced from 18.0 g (0.1 mole) ofN,N-dimethyl-N'-(4-hydroxyphenyl) urea was taken up in 50 ml ofacetonitrile. While stirring, a solution of 17.0 g ofN-methyl-N-phenylcarbamoyl chloride in ml of acetonitrile was added bydrops at 20 to 25 C.

with ammonia or amines.

Some starting products are listed in the following table. (Fp. meansmelting point) i 137.5 1322.50

N-(3-hydroxypheny1)-N-methyl urea Fp N-ethy1N-(3-hydroxyphenyl)-ureaFp.: 135 136C N,Ndimethyl-N'-(3-hydroxyphenyl)-urea Fp.: 190 193CN,N'-dimethyl-N-(3-hydroxyphenyl)-urea Fp.: 123 124C 1 N-(3-hydroxyphenyl)-N,N',N-trimethyl)-urea Fp.: 106CN-(3-hydroxyphenyl)-N,N'-tetramethy1ene-urea Fp.: 138 139CMorpholine-N-carboxylic acid-3-hydroxyanilid Fp.: 180 181C N-(3-hydroxyphenyl )-N'-methylthio-urea F p.: 164C N-ethl-N'-(4-hydroxyphenyl)-urea Fp.: 196 197C N-(4-ydroxyphenyl)-N,N',N'-trimethyl-urea Fp.: 133 CN,N-dimethyl-N-(4-hydroxy-Z-methyl-phenyl)-urea Fp.: 225 227C EXAMPLE 2In loamy soil, monogram seeds of sugar beets as well as Stellaria media,Galisoga parviflora and Senecio vuI-' garis were seeded. The activeingredients were sprayed on the seed in a quantity of 5 kg of activeingredient per hectare, suspended in 600 liters of water per hectare.Then the seeds were covered with earth and allowed to germinate. Theplants came up after days. Even after 4 weeks, no growth damage wasobserved on the sugar beets treated with the agents according to theinvention, while the weeds were destroyed. The known agent, on thecontrary, showed no selectivity for sugar beets.

Sugar solid carriers there enter into consideration for example, lime,kaolin, chalk, talcum, attaclay and other clays. As surface-activesubstances are suitable, among others, salts of the lignin sulfonicacids, salts of alkylated benzenesulfonic acids, sulfonated acid amidesand their salts, polyethoxylated amines and alcohols.

The production of the various preparations can be 3 effected in a mannerknown in the art such as, by grinding or mixing processes.

The herbicidal effect of the agents according to the invention isevident from the following test examples.

Sugar beets, Slellaria media, Galinsoga parviflora, and.

Senecio vulgaris were treated with the agents referred to, after theplants had produced their first foliage leaves and were in the youngstage. The quantity used was 5 kg of active substance per hectare,suspended in 600 liters of water per hectare. With this treatment in thepost-germination process the agent of the invention destroyed only theweeds, while the sugar beets showed no impairment of the growth evenfour weeks after the treatment. The known agent, on the contrary, de-

stroyed also the crop plants.

Stellaria Galinsoga Senecio Sugar Active Ingredient media parvifloravulgaris beets N,N-dimethyl-N'-(3-(N"-(3'-methylphenyl)-carbamoyloxy-phenyl) urea 0 0 l0N,N-dimethyl-N-(3-(N"- tert. butycarbamoyloxy)- phenyl) urea 0 0 0 0Untreated l0 l0 l0 l0 0 totally destroyed I0 not damaged EXAMPLE 4EXAMPLE 1 With a quantity used of 5 kg of active ingredient per hectare,suspended in 600 liters of water per hectare, the following selectivitywas obtained with sugar beets:

Sprayed on seed in Active ingredient pre-germination processN,N-dimethyl-N'-(3-(N"- (3'-methylphenyl)-car- In loamy soil seeds ofpeas as well as Stellaria media, Galinsoga parviflora, and Seneciovulgaris were seeded. The active ingredients were sprayed in a quantityof 3 In post-germmatron process bamoyloxy)-phenyl) urea 100%N,N-dimethyl-N'-(3-(N"- tert. butylcarbamoyloxy)- phenyl) urea 12EXAMPLE 6 At a quantity used of 5 kg of active ingredient per hectare,suspended in 600 liters of water per hectare,

5 the following selectivity was obtained for sugar beets known agentshowed no selectivity. and cotton.

Stellaria Galinsoga Senecio Peas Active ingredient media parvifloravulgaris N,N-dimethyl-N'-(3-(N"- methyl-N 3'-methy1- phenyl)-carbamoy1oxy phenyl) urea 0 0 0 10 F: 126 deg. C

N,N-dimethyl-N'-(3- (N"-tert. butyl-carbamoyloxy)-phenyl) urea 0 0 0 0Untreated 10 10 10 10 0 totally destroyed 10 not damaged Sprayed on seedin pre- 1n post-germ- Active ingredient germination process inationprocess Sugar beet Sugar beet cotton N,N-dimethyl-N -(4-(N"-pheny1carbamoyloxy)- phenyl) urea 100% 100% 100% N,N-dimethyl-N'-(3-(N"-tert. butylcarbamoyloxy)- phenyl) urea 0% 0% 0% EXAMPLE 5 EXAMPLE 7 Inloamy soil seeds of sugar beet (Beta vulgaris) as well as of Sinapisssp. and Solarium ssp. were seeded.

35 On the seeds the active ingredients'were sprayed in a quantity of 5kg of active ingredient per hectare, suspended in 600 liters of waterper hectare. Then the seeds were covered with earth and set up forgermination. The plants germinated after 10 days. Even after 4 40 weeks,no or no considerable growth damage was noted on the sugar beets treatedwith the agent according to Slellaria Galinsaga Senecio Peas Activeingredient media parviflora vulgaris N,N-dimethyl-N'-(3-(N"- methyl-N 3'-methylphenyl )-carbamoyloxy)- phenyl) urea 0 0 0 10 m.p.: 126 deg. C

N,N-dimethyl-N'-(3-(N- tert. buty1-carbamoy1oxy)- phenyl) urea 0 0 0 0Untreated 10 10 10 10 0 totally destroyed 10 not damaged CompoundSinapis ssp. Solarium .rsp. Sugar beets N,N-dimethy1-N'-(4-(N"-phenyl- 00 10 carbamoyloxy )-phenyl) urea N,N-dimethyl-N'-(4-(N"-(3'-methylphenyl)-carhamoyloxy)- phenyl) urea 0 0 l0N,N-dimethy1-N-(4-(N"-methyl- N"-phenylcarbamoyloxy)-phenyl) urea 0 0 8N,N-dimethyl-N-(4-(N"-hexylcarbamoyloxy)-phenyl) urea 0 0 10N,N-dimethyl-N-(3-(N"-tert. butylcarbamoyloxy)-phenyl urea 0 0 0 totallydestroyed 10 no damage 13 the invention, while Sinapis and Solanum weredestroyed. The known agent, on the contrary, showed no selectivity forsugar beets.

EXAMPLE 8 Sugar beets (Beta vulgaris), cotton (Gossypium ssp.), Sinapisssp. and Solanum ssp. were treated with the agents referred to after theplants had produced the first foliage leaves and were in the youngstage. The quantity used was 5 kg of active ingredient per hectare,suspended in 600 liters of water per hectare. With this treatment in thepost-germination process the agents of EXAMPLE 9 Sugar beets (Betavulgaris), cotton (Gossypium ssp.) and Sinapis ssp. were treated withthe agents referred to after the plants had formed the first foliageleaves and were in the young stage. The quantity used was 5 kg of activeingredient per hectare, suspended in 600 liters of water per hectare.With this treatment in the post-germination process the agents accordingto the invention destroyed only Sinapis. The sugar beets and the cottonshowed no or only minor impairment of the growth. The known agent, onthe contrary, destroyed everything.

Compound Sinapis Sugar beets Cotton 0 totally destroyed I0 no damage theinvention destroyed only Sinapis and Solanum. The 35 From the foregoingdescription of the invention as sugar beets and the cotton showed no oronly minor imexemplified and illustrated, it will be noted that wepairment of the growth. The known agent, on the conhave providedherbicides containing N-carbamoyloxytrary, destroyed everything.phenylureas either alone or in conjunction with other Compound SinapisSolarium Sugar Beets Cotton ssp. ssp.

N,N-dimethyl-N'-(4-(N"-phenyl) carbamoyloxy)-phenyl) urea 0 0 l0 l0N,N-dimethyl-N'-(4-(N"-(3'- methylphenyl)-carbamoyloxy)- phenyl) urea 00 l0 l0 N,N-dimethyl-N-(4-(N"-tert. butylcarbamoyloxy)-phenyl)- urea 0 08 l0 N,N-dimethyl-N-4-allylcarbamoyloxy)-phenyl) urea 0 0 l0 l0N,N-dimethyl-N'-(4-(N"-ethylcarbamoyloxy)phenyl) urea l0 l0N,N-dimethyl-N'-(4-(N"-isobutylcarbamoyloxy)-phenyl)- urea 2 2 l0 l0N,N-dimethyl-N'-(4-(N"-propylcarbamoyIoxy)-phenyl) urea 0 0 8 l0N,N-dimethyl-N-(4-(N"-butylcarbamoyloxy)-phenyl) urea 0 O 9 l0N,N-dimethyl-N'-(4-(N"-p-tolylcarbamoyloxy)-phenyl) urea l l l0 l0N,N-dimethyl-N'-(4-(N"-methyl- N"-phenylcarbamoyloxy)-phenyl) urea 0 0l0 l0 N,N-dimethylN-(4-(N"-dimethyl propylcarbamoyloxy)-phenyl) urea 0 0l0 N,N-dimethyl-N'-(4-(N"-hexylcarbamoyloxy)-phenyl) urea 0 0 10N,N-dimethyl-N'-(4-(N"-octylcarbamoyloxy)-phenyl) urea l 0 l0 l0N,N-dimethyl-N-(4-(N"-cyclohexylcarbamoyloxy)-phenyl) urea 0 0 8 l0N,N-dimethyl-N'-(4-(N"-2,3-di methylphenyl )-carbamoyloxy )urea 0 0 l0l0 N,N-dimethyl-N'-(3(N"-tert. butylcarbamoyloxy)-phenyl) urea 0 0 0 0 0totally destroyed I0 no damage herbicides for synergistic effect whichare suitable for weed control in the cultivation of crops.

We claim:

1. N,N-DIMETHYL-N''-(3-(N"-METHYL-N"-(3''-METHYLPHENYL)-CARBOMOYLOXY)-PHENYL-UREA.